Irish moss extract and its production



Patented Feb. 22, 19 49 I a v Y Y I UNITED STATES PATENT OFFICE misnMOSS EXTRACT AND ITS rnonoo'non Mattie P. Hess, Maywood, and Arthur E.Slehrs,

Chicago, Ill., assignors, by mesne assignments, to Krim-Ko Corporation,Chicago, 111., a corporation of Illinois .No Drawing. Application March1, 1945,

Serial No. 580,492

Claims. (cl. ee -142) 1 l I 2 l The current invention relates tocertalnvalusuppressing influence of the salts in the seaable discoveriesin connection with the treatment water. of marine-plants, moreparticularly that type v The current invention provides a procedure forcommonly known as carrageen or Irish moss, th obtaining the heretoforeunknown and therefore .prsent novel procedure resulting in theprodueunavailable product B from the moss in'commertion of a gelose ormucilaginous extract from such clally substantial quantities so that theextract Irish moss, which, when incorporated in a chococan be employed fr its speci pu poses such as with cold milk to provide a suitablestabilized media. for example, eoeee in milk. at a d r v will remainsubstantially-uniformly suspended pharmaceuticalemulslonsice cream andover an i d finit period. all of the uses of Extract A where it isdisadvanwhlch, when incorporated in a chocolate-flavor syrup and thelatter mixed with milk, will exert its maximum suspending effect on thecocoa- .ttampemtures may be usedbut periods of of North America thisunreleased 0r heretofore then {necessary to attam the same unavailablesubstance is primarily Extract B, efiect' However is not possible to mixthis our investigations and experiments having indilateaflavor syrup canbe mixed without heating the suspension of fibrous materials in aqueouschocolate-flavor milkin which the cocoa-particles m Providing a coldProcess chocolatefiavor drink The discovery is based on the theory thatsuch tageous to P t ng or cooking process mosses contain or embody atleast two extractable or Where the vlscosity must maintained substances,hereinafter designated by the letters improved modus Operandi resultingfrom and respectively of different functional the present discoveryprovides a substantial inproperties crease in a valuable productproduced from the moss over that procurable by other procedures.

Such Extract A is gel forming substance The current important revelationis founded on the fact that the refuse or residue resulting fromthesegregation of the extractable substances from y i, Irish moss in aheated or boiling water-solution particles of the drink only after suchmixture of at atmospheric pressure still contains large .milk and syfupis suitably heated s-uch heating amounts of potential product notobtainable by m commercial practices being usually designated 26ordinary means, and, in the case of the large as 145 Fahr. for thirtyminutes, although lower majority of mosses grown m the coastal waters'type of chocolate-flavor syrup containing Extract cated that thissource of Extract B is locked up A with mixture that is, example, within the fibers of the residue in such a manner as .Imilk at Fahrand haveSuspension f the to prevent its procurement by heat at 212 F.

c a-P t 0 in t resulting p Considered somewhat differently, ourinvention, I On the Othe a d, ct provides its re particularly, refers towater-extractions of lmlamolmt maxlmum Suspendlng Sustain- Irish mosswhose dried solids react with some of ins e t when t c vo y up theconstituents of cold milk to provide the retainlng it is mixed with coldmilk at about 36 quired stabilizing effect.

'Fahr. and, in this case, this different extract B It is therefore oneof the principal objects of w ll imm diat y egin to apply its suspendingour invention to provide a form of dried extract p wer and it is possile o o t i thereby 40 ofiering the valuable thickening and stabilizingmercially-sta'ble chocolate-flavor milk without the properties inherent,in Irish moss, a further purnecessity of applying heat as is required inthe pose of the invention being to provide a stabilizcase of the use OfE act A. ing substance made from Irish moss-which may be Differentmosses, or the same mosses grown introduced directly into dairy productcomposiunder different conditions of nutrition and temtions withoutmodification of the usual manufac- ,perature, or asingle moss in varyingstages of turing procedures or the subjectin of the comdevelopment, mayyield different amounts of the positions to heating. extracts A and B,it being borne in mind, that Another important aim of'the invention isto normally, neither the sources .of extract A nor B utilize profitablythe by-productextractlon reslare soluble in sea-water, probably becauseof the b0 dues resulting from the preparation of the conmoss.

ventional Irish moss extracts, an added salient feature of the inventionbeing to increase the total yield of commercially-utilizable extractthat may be obtained from the Irish moss.

If the moss is-subjected to the action of hotwater at a temperature, forexample, from 180 Fahr. to 212 Fahr. substantially all of the Extract' Awill be withdrawn therefrom and form a solution with the water, and, inaddition, an amount of the substance B will be extracted and. also gointo the solution, but the amount of Extract B in such solution willdepend upon the quantity thereof which is free to be extracted 'into ahot water-solution at atmospheric pressure.

If this aqueous double-extract of the moss is then dried to a solid, orif the solubledouble-extract is prepared in dry form by any convenientmeans, the resulting product will have the properties of Extract A andExtract B in proportion to the percentages of these substances presentin the dried product. So far as is known, up to the present time,neither Extract A nor Extract B has been isolated by anyone except thepresent inventors. I

It is highly desirable to produce Extract B in as pure a form aspossible, because in numerous cases the presence of Extract A isdetrimental to the use of the Irish moss extract when the Extract Bproperties alone are desired.

An example of this, as indicated above, is the case of achocolate-flavor syrup which is designed to be mixed, without heating,with cold to obtain the desired cold suspending strength.

As the proportion of Extract A becomes greater in the dried extract, thesyrup becomes too thick to be useful commercially and the cost of thestabilizing-agent becomes greater. For this reason, it is highlydesirable to have a dried Extract B in as pure a state as possible, sothat the resulting chocolate-syrup in which it is used will be very thinand the amount of stabilizing or suspending agent required will be low.

We have been able to obtain such a dried Extract B by following eitherone of two procedures: (1) subjecting the residues of prior 180 Fahr.extraction to further extraction and at greater thanatmospheric-pressure, or (2) treating the residues of prior 180 Fahr.extraction chemically by a suitable re-agent, such as sulfite, in'theproper manner, and subsequently extracting at a temperature such, forinstance, as 180? Fahr., this second procedure constituting the subjectmatter of our.copending patent application Se rial No. 787,476. filedNovember 21, 1947.

In following the first, above-mentioned. supplemental procedure, theIrish moss is in tially subjected to water-extraction by theconventional procedure. using a temperature, such as 180 Fahr.. so thatall of its Extract A and as much of its Extract B as is segre atableunder such'con ions is removed or extracted from the This extractionmaybe repea ed a second t me to be sure to remove all of the Extract Apossible. The moss residue and water are then subjected to about fifteenpounds pressure above atmospheric-pressure in an autoclave for a peri.0d of about one hour, this being a practical length of time giving goodresults, the use of a lesser pressure even for longer periods of timeresulting in decreased yields, whereas greater pressures are aseffective in shorter periods of time.

Experiments along the line indicated above are shown in the table.

Table Temperature of Viscosity of Cold Milk Extraction Tune I YieldUsing a 0.6% Syrup Per cem \IIVhoAeMoss: 180 F.. 60 min.. 65 20.0Seconds-settling.

es: ue:

180 F 60 min. 51.8 25.0 Seconds.

212 F. 60 min 53.2 37 Seconds. 227 F., 5# Pressure.- 60 min. 46.0 58Seconds. 244 F., 121! Prcssure 5 min". 17.0 89 Seconds. g l2 gressureu5mg gecongs.

. ressure m econ s.

244 12# Pressure... 60 min 56 76 Seconds. 214 F., 12!; Pressure. 90 min-70 34 Seconds. 244 F., l2# Pressure" 2 his-.. 54 36 Seconds. 244 F., l2#Pressure" 3 hrs 43.6 29 Seconds-Settling. 252 F., 161! Pressure 15 min.54.8 60 Seconds. 252 F., 16# Pressure. 30 min 58.0 87 Seconds. 252 F.,l6# Pressure" 60 min. 62.8 64 Seconds. 252 F., 16# Pressure. 2 hrs 56. 838 Seconds-Settling.

These experiments were carried out by first thoroughly washing the raw,whole, unwashed, Irish moss and then extracting at 180 Fahr. for onehour in an approximate 3% water-soluble, three pounds of moss being usedwith 97 pounds of water. At the end of this time, the extracted materialwas drained away from the moss residue and the latter washed thoroughlywith warm water, drained again, and such residue then dried in ashelf-dryer employing a fan and hotair. Enough of this extract wasprepared at one time so that'it could be used in the complete set ofexperiments. This dried residue was then mixed with water to form a 4%solution and extracted 'at various temperatures and pressures fordifierent periods of time, the material during such treatment beingagitated toassu're uniform extraction. After extraction the liquid wasfiltered and such liquid extract dried and powdered.

Tests were carried out on the dried powdered extract and are reported inthe table, the method of testing the extract being to use the driedmaterial in making up a cold mixed chocolate-flavor syrup using 0.6% byweight of the stabilizer to be tested, mixing such chocolate-flavorsyrup with milk under a standard procedure and then determining whethersettling of the cocoa-particles occurred and determining the viscosityof the finished chocolate-flavor milk (right-hand column) The tableshows in its first line that when an extract was made from blackScituate moss at Fahr. for sixty minutes a yield of dry extractconstituting 65% by weight of the amount of dry moss employed wasobtained, but such extract showed no cold-mix properties.

When, however, an extract was obtained, from the residue of thepreceding extraction, during a period of sixty minutes at 180 Fahr., ayield of 51.8% of the moss was extracted but again such extract showedno cold-mix properties. When such an extraction was carried out at 212Fahr. an extract yield of 53.2% was had and cold-mix properties began toappear in the extract as indicated by the 37 seconds.

When the temperature was raised to 227 Fahr. and a pressure of 5 pounds,above atmospheric pressure, per square-inch was used a yield of 46% wasobtained in 60 minutes and the cold-mix properties raised quite markedlyas shown by a inch above atmospheric pressure for 60 minutes the yieldincreased slightly to 62.8% but there was a no significant change in thestrength of the extract, this seeming to indicate that if the extractiontime is kept to sixty minutes that there is not much difference between244 and 252 Fahr.

There is no over-all increase in strength or yield with increasingtemperatures and there is no indication that the cold-mix properties maybe destroyed faster at 16 pounds pressure per square-inch, at 252 Fahn,than is the case of 12 pounds pressure per square-inch and 244 Fahr.

With respect to the influence of time on the extraction, it appears asthough there is a definite curve for each temperature, in which theyield and strength reach a maximum and then taper off with increasingtime.

It is seemingly of the essence of our discovery that the refuse orfibrous residues, resulting from the prior extraction of crude Irishmoss with hot or boiling water still contain large amounts of colloidalsubstance of high. viscosity and stabilizing capacity which is notrecoverable by ordinary methods. Whether this substance characterized asExtract B herein is initially locked up in the fiber of the moss in amanner which precludes its extraction by a simple boiling, or is somenew cleavage product formed from the fiber or from some other initiallyinsoluble substance not initially obtainable is at present con-.lectural.

We have found that the Irish moss exhausted residues ofboiling-water-extractions may be made to yield, under suitableconditions of processing, large increments of extract not heretoforeobtainable either from the residues or from the whole moss by any of theusual known means.

Our novel process comprises subjecting the moss residue to aqueousextraction under conditions which favor molecular or structural cleavagewhile at the same time inhibiting hydrolysis in each of the twoindicated supplemental procedures, the reaction, whatever it may be,being evidenced by a profound physical change in the moss refuseundergoing extraction in that it loses its brittleness and becomes softand pliable and, with the release of the colloidal principle, thesurface of the moss becomes slimy to the touch, these changes notoccurring when exhausted moss fiber is boiled in water in the usualmanner.

This is seemingly evidence of a chemical change in the colloidalconstituents of the treated residue.

As indicated in the table, this is apparently borne out by theestablished fact that although the percentage yield from the residue isapproximately the same (53.2) at 212 F. at atmospheric pressure as that(54.8) at 252 F. at 16 pounds pressure above atmospheric pressure, theformer having practically no cold-mix properties (37 seconds) whereas,the latter has excellent coldmix characteristics (60 seconds).

About 0.5% to 1.0% of the weight of the syrup All cold mixed syrups nowin the trade can be used either cold or hot but not necessarily equallyfavorably.

If the syrup contains only Extract B then the syrup can be usedsatisfactorily either hot or cold,

but if the syrup also contains an appreciable amount of Extract A thenit cannot be gratifyingly used with heated milk, the reason being thatwhen a syrup containing Extract A is heated with milk and subsequentlycooled, the product may be too thick to be satisfactory commercially.one distinction between Extracts A and B being that the former is agelling agent and the latter a nongelling agent.

It is seemingly new to provide a product co sisting of Extract B only,either in the form of powder, or dissolved in water, or dissolved inchocolat syrup. I In passing, it may be mentioned that the ashcontent,by which is meant the weight of material remaining after Extract B hasbeen burned, of this new product obtained by the pressure-extraction isdesirably much lower than in Irish moss extracts prepared by any otherknown means up to the present time. This is also true of the nitrogenousand fatty materials.

Moreover. Extract A is probably a colloidal substance plus othercolloidal or non-colloidal substances which may modify the properties ofsuch extract, whereas Extract colloidal.

We claim:

1. The carbohydrate Irish moss extract characterized by the fact thatwhen a quantity thereof, corresponding to approximately 2.6 gramsthereof in dry powdered form, is added to and thoroughly intermixed with16 ounces of 36 Fahr'. milk such extract will within about thirtyseconds begin to apply its suspending and thickening power to the milk,such extract being derived from Irish moss residue which has beenpreviously freed from at least 80% of all Irish moss constituentsextractible from the moss by hot fresh water at atmospheric pressure, bysubjecting such residue to supersaturated steam at a' pressure betweenabout five pounds and fifty pounds per square inch above atmosphericpressure.

2. The carbohydrate Irish moss extract dissolved in syrup in the ratioof about /z% to 1% of B is seemingly purely the weight of the syrupcharacterized by the fact that when one part by volume ofsuchextractcharged syrup is added to and thoroughly intermixed with aboutten parts by volume of 36 Fahr. milk such extract will within aboutthirty seconds begin to apply its suspending and thickening power to themilk, such extract being derived from Irish moss residue which has beenpreviously freed from at least 80% of all Irish moss'constituentsextractible from the moss by hot fresh water at atmospheric pressure, bysubjecting such residue to supersaturated steam at a pressure betweenabout five pounds and fifty pounds per squareinch above atmosphericpressure. 7

3. The novelprocess of extracting a carbohydrate product by subi eatingthe Irish moss residue, which has been previously freed fromsubstantially all of the constituents of the Irish moss extractible byfresh hot water at atmospheric pressure, to the action of supersaturatedsteam at a pressure of about 5 pounds to 50 pounds per square-inch aboveatmospheric pressure.

tractible by fresh hot water at atmospheric pres- 6 whichsaidsupersaturated steam is applied to said 10 1 2,462,898 4 Th 7 v I v8 e novel process of extracting a carbohydrate product by subjecting theIrish moss residue, REFERENCES CITED 7 which has been previously freedfrom at least 80% The following references are of record in the of allof the constituents of the Irish moss exfile of this patent:

sure, to the action of supersaturated steam at a I I: STATES PATENTSpressure of about 5 pounds to 50 pounds per Number ame Date square-inchabove atmospheric pressure. 2,337,562 Lund Dec. 28, 1943 5. Thenovelprocess set forth in claim 3, in OTHER REFERENCES residue for a periodof about one hour. Jour. Chem. Soc. (London), 1943, pages 51-54.

MATTIE P. HESS. ARTHUR E. SIEHRS.

